Cd 1 − x Zn x Te alloys have been studied by surface photovoltage spectroscopy (SPS) and energy dispersive spectroscopy (EDS). The analyses of surface photovoltage spectra have been perfomed at near and above band gap energies. Surface recombination effects on the surface photovoltage have been investigated. SPS analyses of Cd1−xZnxTe alloys with different surface conditions have shown that the surface recombination velocity significantly affects the SPS determination of the material band gap. Accounting for this and preparing the surfaces accordingly, SPS spectra of Cd1−xZnxTe samples have allowed an accurate determination of the optical band gap as a function of the Zn concentration, determined via EDS analyses. The local increases in the density of states associated with band structure features in Cd1−xZnxTe alloys have been investigated by SPS spectra in the above band gap energy range.